Synthetic production of methanol



Aug. 8, 1933. R. s. RICHARDSON SYNTHETIC PRODUCTION OF ETHANOL OriginalFiled April 24. 1925.

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6A5 INLET cmLYsT Patented Aug. 1933 UNITED STATES PATEN OFFICE 1,921,176smnarrc PRODUCTION or METHANOL Ralph S. Richardson, Teaneck, .N. 1.,assignor to Nitrogen Engineering Corporation, New York, N. Y., aCorporation of New York I Original application April 24, 1925, SerialNo.

25,590, now Patent No. 1,704,214.

Divided and thlsapplication December 12, 1928. 'Serial No.

1a cam (o1'. 260-156) ticularly my invention comprises novel processesin the manufacture of'valuable products by direct synthesis from theircomponent gases which are passed athigh temperatures under pressure overa catalyst mass, as for example, the manufacture of methyl alcohol ormethanol (CH3.'OH) from carbon monoxide (CO) and hydrogen. In anyinstance the elements should be combined in their respective proportionsin the gaseous mixture and then compressed to relatively high pressuresand passed under such pressure over a suitable catalytic agent capableof stimulating the combination of the two gases whereby sumcient heat isproduced to maintain the temperatures required for satisfactory yields.

In the manufacture of methanol from a mixture of one part of carbonmonoxide andtwo parts of hydrogen by volume which is preferably passedunder 300 atmospheres pressure and at a high temperature (300 to 400 C.)over a catalyst containing metallic copper and -.zinc oxide withrecirculation of the uncombined gases, success depends almost entirelyon the regulation and control of the temperatures maintained in thecatalytic chamber.

In industrial operations many difliculties are' reaction unless theingoing gas mixture is pre-- heated either directly or by the hotoutgoing mixture after conversion through heat-exchange apparatus,either separately installed or arranged within the catalyst chamber. r

Furthermore in industrial practice on a-commercial scale, it has beenfound that the portion of the catalyst which first comes in contact withthe gas mixture where the activity is more intense, may become injuredby overheating or even poisoned by impurities in the gases. Even thoughsuch heat is removed by suitable cooling surfaces surrounding thatportion of the catalyst, yet local overheating is likely to occur in thecatalyst mass. Hence it follows that the maximum life of a catalyst aswell as maximum conversion of the methanol products are largelydependent upon the temperature at which such catalyst operates inproducing methanol as .I have stated.

Heretofore removal of the heat of reaction has been accomplishedthroughout the catalyst in practice by use of heat transfer surfacessuitably disposed within the catalyst mass, but such system of controlinevitably permits great differences in temperature in various isolatedparts of the catalyst mass, and especially allows no ade-. quate controlof temperature capable of being varied with operating conditions'tosecure optimum temperaturesfor maximum conversion.

According to my invention 1 control. the temperature throughout thecatalyst mass in varying sections or zones by which the temperature inthe major portion which is last to be reached by the proper gaseousmixture is maintained closely to the optimum temperature for maximummethanol conversion, since the greater part of the heat generatedthrough the reaction is liberated in the lesser portion of the catalystmass which initially comes in' contact with the gas mixture entering thecatalyst furnace. The temperature control may be attained by passingcomparatively cool gas at various pointswithin the converter to becirculated therein. Furthermore the temperature in the first sectionorfportion of the catalyst mass is controlled partly by introducing partof the inflowing gas beyond a portion of the heatexchange surfaceusually attached to the catalytic furnace and partly by the transfer ofheat from the catalyst itself to the incoming flow of the gas mixture,while the temperature of the second, and preferably 'the major, portionof 'the catalyst mass iscontrolled by the admixture of cooler gas tothat superheated gas leaving the first section or portion of thecatalyst.

According to another aspect of my invention, the temperature and amountof gas mixture entering the second or final portion of the catalyst massare also controllable'by a selective arrangement orsystem forlay-passing the inflowing gas mixture partially or altogether from theheat exchanger. Such method of temperature control allows not only acloser regulation of temperatures for thefinal catalytic operation withthe maximum yield of product, but'also permits less expensiveconstruction than the internal system for cooling the catalystheretofore used.

In carrying out my invention the catalyst mass is preferably separatedinto two or more separate portions and are preferably arranged in tandemwithin the catalytic furnace and coupled together with one or moresections of heat-interchangers also arranged in tandem so that all theinflowing or entering gas mixture may go either in series through theapparatus including the two or more separate portions of catalyst or, ifdesired, the entering gas mixture may be predeterminedly directed byseparate connections and regulating cocks with the gas supply that allor any portion of the gas mixture may by-pass either (1) a part or allof the heat interchanger system; or (2) all or any portion of such gasmixture may by-pass all the heat-interchanger system and the firstportion or section of the catalyst mass, While maintaining a continuouscirculation of the gas mixture through both catalyst mass andheat-interchanger with a substantial uniformity of pressure during thepassage of the gas mixture from one portion to the next succeedingportion of the catalyst mass.-

The accompanying drawing represents in vertical section an apparatusadapted for carrying out the process of my invention.

The catalyst furnace 1 is arranged in the upper part of the cylindricalvessel 2 having the top 3 and bottom 4 strong enough to withstand thehigh pressures employed. The furnace 1 is preferably divided into twoparts by the perforated grate 5 which is preferably located somewhatabove the middle of the furnace 1 to form the upper catalyst chamber 6containing the catalyst substance 7, with the lower catalyst chamber 8containing the major portion of the catalyst substance 9 resting on theperforated grate 10- forming the bottom of the furnace 1. arrangement ofthe two catalyst chambers 6 and 8 is preferably in tandem withthechamber 8 somewhat larger in content than the chamber 6 as will behereinafter explained. The heatinterchanger 11 is preferably locatedbelowthe catalyst furnace 1 as shown; such interchanger comprises twosections 12 and 13 also arranged in tandem, the head 14 of the section'12 having the pipe 15 connected therewith and extending upwardlythrough the furnace 1 and opening into the top of the chamber 6 abovethe catalyst '7. The sections 12 and 13 each comprises a series ofvertically-disposed spaced-apart pipes-16 extending therethrough withthe chamber 1'7 located between the two sections 12 and 13. The bottomof the section 13 is formed with the head 18 connected by the pipe 19extending through the bottom 4 and connecting with the gas inlet pipe 20communicating by the cook 21 withthe source of the ingoinggas mixtureflowing upwardly through the pipe-22. To by-pass and control the volumeof the inflowing gas mixture from the pipe 22 to different portions ofthe.

apparatus, the pipe 23 having the cock 24 therein communicates with thechamber 1'7; also the pipe 25 having the cook 26' communicates with thehead 14; while the upper end of the pipe 22 is connected with the pipe27 leading to the upper part of the catalyst chamber 8, such pipe havingthe cock 28 to control the flow of gas through the pipe 27. The top 3 isformed with the bore' 29 connected with the gas outlet pipe 30. In thedrawing the arrows with the solid lines indicate the path of the gasmixture going to and through the furnace 1, while the arrows with thebroken As shown the lines show the path of the gas mixture after passingfrom the catalyst furnace.

When using the form of apparatus as illustrated, the procedure ofcontrolling the direction and volume of ingoing gas mixture to difierentparts of the apparatus from the pipe 22 is determined by the selectivemanipulation of the several cocks 21, 24, 26 and 28. The essentials ofthe arrangement shown comprise the two separate portions of catalystsubstance '7 and 9 with one or more sections 12 and 13 of theheat-interchanger set up in tandem so that all the inflowing gas mixturemay go in series through all the equipment including the two catalystportions 7 and 9, or if so desired, by means of the separate pipeconnections and cocm connected with the gas inflow in the pipe 22, suchinflowing gas may be so directed that all or any portion thereof mayby-pass (a) a part or all of the heat-interchanger 11, or (b) the entireinterchanger system and the catalyst chamber 6. The separate gas inletconnections through the pipes 20, 23, 25 and 27, each with its suitablecock, also permit the gas to enter the interchanger 11 at one or morepoints, as well to the twocatalyst chambers 6 and 8.

1 One advantage of having the upper and initially-contacted catalyst 7of less content than the final catalyst 9, is that the temperature inthe larger'portion 9 of the catalyst mass may be held closely to theoptimum, since the greater part of the heat reaction is liberated in thechamber 6 throughout the catalyst 7. Furthermore the temperature in thecatalyst mass '7 may also be controlled partly by by-passing part of theheat-interchanger surface and partly by transfer of heat from thecatalyst mass to the incom-v ing gas. The temperature of the catalystmass 9 in the chamber 8 may also be controlled by the admixture ofcooler gas to theigas leaving the upper catalyst 7, and the temperature.of gas entering the final catalyst 9 is also controllable by theselective arrangement for by-passing partor all of the interchangersystem 11. 1

Neither the size, shape or arrangement of the heat-interchanger andcatalyst chamber is .essential; a convenient form, as shown, locates theinterchanger in the lower part of the containing cylindrical vessel 2with two separate catalyst bodies in series above the interchangers andwithin the same vessel 2.

The gas mixture introduced into the circulating system as hereinbeforedescribed refers to the unheated carbon monoxide and hydrogen mixturehaving some methanol therein that is passed into the circulating gasflow. before reaching the catalyst or any part'thereof. v

I wish it to be understood that the invention is not to be confined tothe-method shown for effecting the improvements, as such method may bevaried in many ways without departing from the nature of the inventionand without sacrificing its chief advantages.

I claim as my inventioni 1. In the process of producing methanol bypassing a gaseous mixture of carbon monoxide and hydrogen over acatalyst mass at high temperatures under pressure, the step which com'2. In the process of producing methanol bypassing a gaseous mixture ofcarbon monoxide and hydrogen over va catalyst mass at high temperaturesunder pressure, the stp which comprises introducing gas at a lowertemperature in predetermined amounts to separated portions of differentcontent of the catalyst mass while maintaining a continuous circulationtherethrough.

3. In-the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high teniperaturesunder pressure, the step which comprises varying the amount of inflowinggaseous mixture to separated portions of different content of thecatalyst mass while maintaining a continu ous circulation therethrough.

4. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high tem peraturesunder pressure, the step which comprises varying the amount of infiowinggaseous mixture at a lower temperature to separated portions 'ofdifferent content of the catalyst mass while maintaining a continuouscirculation therethrough.

5. In the process of producing methanol by passing a gaseous'mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperaturesunder pressure, the step which comprises introducing gas inpredetermined amounts to separated portions of different content of thecatalyst mass while maintaining a continuous circulation therethroughand a substantial uniformity of pressure during the whole of theoperations.

6. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperaturesunder pressure, the step which comprises varying the amount of infiowinggaseous mixtureto separated portions of different con-'- and hydrogenover a catalyst mass at high temperatures under pressure, the stepwhichcomprises introducing gas at variably lower temperatures inpredetermined amounts to separated portions of different content of thecatalyst mass while maintaining a continuous circulation therethrough.

8. In the process of producingmethanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperaturesunder pressure, the step which comprises varying the amount of inflowinggaseous mixture at variably lower temperatures to separated portions ofdifferent content of the catalyst mass while maintaining a continuouscirculation therethrough. H

9. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 400 atmospheres, the steps which comprise passingthe gas mixture into direct reaction contact with a portion of thecatalyst mass, and then introducing additional, comparatively coolercarbon monoxide hydrogen mixture to the reacted'gas flow from saidportion in controllable amounts before such combined flow is passedthrough other spaced-apart portions of the catalyst of variably greatercontent from said first catalyst portion for further reaction whilemaintaining a continuous circulation therethrough.

l0. In the process of producingimethanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 100-atmospheres,

the steps which comprise passing the gas mixture into direct reactioncontact with a portion of the catalyst mass, and then introducing.additional comparatively cooler carbon monoxide-hydrogen I mixture at asubstantial uniformity of pressure to the reacted gas flow {from saidportion in controllable amounts before 'such combined flow is passedthrough other spaced-apart portions of the catalyst of variably greatercontent from said first catalyst portion for further reaction whilemaintaining a continuous circulation there-' through.

11. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 400 atmospheres, the steps which comprise passingthe gas mixture into direct reaction contact with a portion of thecatalyst mass, and then introducing variable quantities of comparativelycooler carbon monoxide-hydrogen mixture to the reacted gas flow fromsaid portion in controllable amounts before such combined flow is passedthrough other spaced-apart portions of the catalyst of variably greatercontent from said first catalyst portion for further reaction whilemaintaining a continuous circulation therethrough.

'12. In the process of producing methanol by passing a gaseous mixtureof carbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 400 atmospheres, the steps which comprise passingthe gas mixture intodirect reaction with a portion of the catalyst mass,and then introducing variable quantities of comparatively cooler carbonmonoxide-hydrogen mixture at a substantial uniformity of pres sure tothe reacted gas fiow from said portion in controllable amounts beforesuch combined flow is passed through other spaced-apart portions ofpassing a gaseous mixture of carbon monoxide and hydrogen over acatalyst mass at high temperature under pressure below 400 atmospheres,the steps which comprise passing the gas mixture into direct reactioncontact with a portion of the catalyst mass, and then introducingadditional comparatively cooler carbon monoxide-hydrogen mixture to thereacted gas flow from said portion in controllable amounts before suchcombined flow is passed through other spaced-apart portions of thecatalyst of variably greater content from said first catalyst portionfor further reaction while maintaining a continuous circulationtherethrough and a substantial uniformity of pressure during the passageof said gas mixtures successively through said spaced-apart portions ofthe catalyst mass. v

14. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst .mass at hightemperature'under pressure below 400 atmospheres the steps whichcomprise passing the gas mixture spaced-apart portions of the catalystof variably greater content from said first catalyst portion for furtherreaction while maintaining a continuous circulation 'therethrough and asubstantial uniformity of pressure during the passage of said gasmixtures successively through said spaced-apart portions of the catalystmass.

15. In'the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 400 atmospheres, the steps which comprise passingthe gas mixture into direct reaction contact with a portion of thecatalyst mass, and then introducing additional comparatively coolercarbon monoxide-hydrogen mixture to the reacted gas flow from saidportion in controllable amounts before such combined flow is passedthrough other spaced-apart por tions of the catalyst of variably greatercontent from said first catalyst portion for further re-' action, saidcontrollable amounts being brought indirectly into contact with saidspaced-apart portions of the catalyst, while maintaining a con tinuouscirculation therethrough.

16. In the process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperatureunder pressure below 400 atmospheres the steps which comprise passingthe gas mixture into direct reaction contact with a portion of thecatalyst mass, and then introducing variable quantities of comparativelycooler carbon monoxide-hydrogen mixture of reacted gases, to the reactedgas flow from said portion in controllable amounts before such combinedflow is passed through other spaced-apart portions of the catalyst ofvariably greater content from said first catalyst portion for furtherreaction, said controllable amounts being brought. indirectly intocontact with said spaced-apart portions of the catalyst,- whilemaintaining a continuous circulation therethrough.

17. The process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperaturesunder pressures below 400 atmospheres, which comprises first passingcarbon monoxide hydrogen mixture through a separated portion of thecatalyst mass, then introducing variable quantities of comparativelycooler carbon monoxide-hydrogen mixture to the outfiowing mixture ofreacted gases, and thereafter passing the combined gas flow mixturethrough another tent than said first-mentioned portion with asubstantial uniformity of pressure maintained throughout said passagethrough said portions of the catalyst.

18. The process of producing methanol by passing a gaseous mixture ofcarbon monoxide and hydrogen over a catalyst mass at high temperaturesunder pressures below 400 atmospheres, which comprises first passingpreheated carbon monoxide-hydrogen mixture through a separated portionof the catalyst mass, then introducing cooler carbon monoxide-hydrogenmixture to the outflowing mixture and thereafter passing the combinedgas flow mixture through another separated portion of the catalyst ofgreater content thansaid first-mentioned portion with a substantialuniformity of pressure maintained throughout said passage through saidportions of the catalyst.

RALPH S. RIQHARDSON.

separated portion of the catalyst of greater con-

